Effect of promoters for n-butane oxidation to maleic anhydride over vanadium–phosphorus‐oxide catalysts: comparison with supported vanadia catalysts

The oxidation of n-butane to maleic anhydride was investigated over model Nb‐, Si‐, Ti‐, V‐, and Zr‐promoted bulk VPO and supported vanadia catalysts. The promoters were concentrated in the surface region of the bulk VPO catalysts. For the supported vanadia catalysts, the vanadia phase was present as a two‐dimensional metal oxide overlayer on the different oxide supports (TiO₂, ZrO₂, Nb₂O₅, Al₂O₃, and SiO₂). No correlation was found between the electronegativity of the promoter or oxide support cation and the catalytic properties of these two catalytic systems. The maleic anhydride selectivity correlated with the Lewis acidity of the promoter cations and oxide supports. Both promoted bulk VPO and supported vanadia catalysts containing surface niobia species were the most active and selective to maleic anhydride. These findings suggest that the activation of n-butane on both the bulk and supported vanadia catalysts probably requires both surface redox and acid sites, and that the acidity also plays an important role in controlling further kinetic steps of n-butane oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

A comparative study on liquid phase alkylation of 2-methylnaphthalene with long chain olefins using different solid acid catalysts

A comparative study has been made over a variety of solid acid catalysts, which include isopoly and heteropoly ions supported on various supports such as zirconia, titania, a large variety of zeolites and a couple of mesoporous materials for liquid phase alkylation of 2-methylnaphthalene with 1-octene. All the catalyst systems were characterized by nitrogen sorption analysis, X-ray diffraction and NH₃-TPD. Inspite of their high acid amounts zeolites gave poor catalytic performance due to their diffusional constraints; on the other hand mesoporous materials lacked diffusional constraints but due to their low acid amounts resulted in poor conversions. Isopoly and heteropoly ions supported on zirconia and titania were found to be catalytically active for the reaction due to total surface acidity. Among them, isopolytungstate supported on zirconia exhibited the best catalytic activity and was used for further optimization of reaction conditions. Excellent conversions of all olefins (>92%) with high selectivity of monoalkylmethylnaphthalene (>95%) was obtained under optimized reaction conditions. The catalyst could be recycled for several times without any obvious loss of its activity.     

Selective oxidation of propane on MgO/γ‐Al2O3‐supported molybdenum catalyst: influence of promoters

The influence of promoters, potassium and samarium, on molybdenum supported over MgO–γ‐Al₂O₃ catalyst has been investigated in the oxidative dehydrogenation of propane. The acidities of catalysts were determined by temperature‐programmed desorption of NH₃ and by decomposition of 2‐propanol. The K‐promoted catalyst showed the lower acidity followed by the Sm, whereas the unpromoted sample showed the highest acidity. The higher the acid character of the catalyst, the lower the selectivity to propene. Redox properties determined from EPR spectra change with the addition of the promoter. A parallelism between Mo⁶⁺ reducibility and catalytic activity was found. This revised version was published online in July 2006 with corrections to the Cover Date.     

New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-41

New solid acid catalysts, consisting of heteropoly acid (HPA) H₃PW₁₂O₄₀ (PW) supported on a mesoporous pure-silica molecular sieve MCM-41, have been prepared and characterized by nitrogen physisorption, X-ray diffraction, FT-IR, and³¹P magic angle spinning NMR. The PW/MCM-41 compositions with PW loadings from 10 to 50 wt% have 30 Å uniformly-sized mesopores. HPA retains the Keggin structure on the MCM-41 surface and forms finely dispersed HPA species. No HPA crystal phase is developed even at HPA loadings as high as 50 wt%. PW/MCM-41 exhibits higher catalytic activity than H₂SO₄ or bulk PW in liquid-phase alkylation of 4-t-butylphenol (TBP) by isobutene and styrene. In the alkylation of TBP by styrene, PW/MCM-41 shows a size selectivity compared to bulk PW and PW/SiO₂, providing higher yields of a 2-(1-phenylethyl)-4-t-butylphenol, at the expense of the more bulky 2,6-bis-(1-phenylethyl)-4-t-butylphenol. The PW/MCM-41 compositions, having strong acid sites and a regular mesoporous system, are promising catalysts for the acid-type conversion and formation of organic compounds of large molecular size.     

Regeneration behaviors of Fe/Si‐2 and Fe–Mn/Si‐2 catalysts for C2H6 dehydrogenation with CO2 to C2H4

The catalytic performance of Fe/Si‐2 and Fe–Mn/Si‐2 catalysts for conversion of C₂H₆ with CO₂ to C₂H₄ was examined in a continuous‐flow and fixed‐bed reactor. The results show that the Fe–Mn/Si‐2 catalyst exhibits much better reaction activity and selectivity to C₂H₄ than those of the Fe/Si‐2 catalyst. Furthermore, the coking–decoking behaviors of these catalysts were studied through TG. The catalytic performances of the catalysts after regeneration for conversion of C₂H₆ or dilute C₂H₆ in FCC off‐gas with CO₂ to C₂H₄ were also examined. The results show that both activity and selectivity of the Fe–Mn/Si‐2 catalyst after regeneration reached the same level as those of the fresh catalyst, whereas it is difficult for the Fe/Si‐2 catalyst to refresh its reaction behavior after regeneration. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbonyl‐precursor‐based W/Al2O3 and CoW/Al2O3 catalysts: characterization by temperature‐programmed methods

Carbonyl‐precursor‐based W/Al₂O₃ and bimetallic CoW/Al₂O₃ catalysts were prepared by gas‐phase adsorption in a fluidized‐bed reactor. The surface species formed during the gradual and controlled preparation process were studied by temperature‐programmed methods. Interactions on the surface were investigated as a function of metal loading by temperature‐programmed oxidation (TPO) and oxygen pulse chemisorption (PCO). A clear relationship was observed between decarbonylation treatment and the tungsten species formed. Total acidity of the samples was determined by temperature‐programmed desorption of ammonia (NH₃‐TPD). The NH₃‐TPD measurements, together with previous activity studies, suggest a relationship between total acidity and hydrotreating activity. The results of PCO and NH₃‐TPD measurements indicate that when the controlled gas‐phase preparation method is applied to zerovalent carbonyl precursor, the unfavourable formation of tungsten oxide can be minimized. This revised version was published online in July 2006 with corrections to the Cover Date.     

In situ UV‐VIS diffuse reflectance spectroscopy of reduction–reoxidation of heteropoly compounds by methanol and ethanol: a correlation between spectroscopic and catalytic data

The degree of reduction/oxidation of H₄PVMo₁₁O₄₀ (HPA) and Cs₂H₂PVMo₁₁O₄₀ (CsPA) was studied during reduction and reoxidation by methanol, ethanol and mixtures with oxygen, respectively. The peak intensity of the intervalence charge transfer (IVCT) band, the apparent band gap energy (E _g ^* ) and catalytic data were obtained by in situ UV‐VIS diffuse reflectance spectrosccopy (UV‐VIS‐DRS) and on‐line gas chromatography (GC), respectively. The peak intensity of the IVCT band and E _g ^* increase during the reduction of heteropoly compounds by the alcohols. The spectroscopic and catalytic data (conversion, selectivity) correlate in the transient state during the reoxidation process. It is shown that isolated Keggin anions act as precursors for the active states of the catalysts, which molecular structure cannot be deduced from UV‐VIS spectroscopy alone. UV‐VIS spectroscopy, however, can serve as a tool to determine the degree of reduction in future combined in situ UV‐VIS/Raman/XRD studied. This revised version was published online in July 2006 with corrections to the Cover Date.     

129Xe NMR study of 12-tungstophosphoric heteropoly acid supported on silica

The structure of 12-tungstophosphoric heteropoly acid (H₃PW₁₂O₄₀) supported on silica has been studied by¹²⁹Xe NMR of adsorbed xenon. The¹²⁹Xe NMR spectra are found to depend on the surface HPA concentration. The¹²⁹Xe NMR data provide evidence for the presence of an organized microporous structure within HPA overlayers. These results are in agreement with nitrogen adsorption and capillary condensation (77 K) measurements. The high sensitivity of the¹²⁹Xe NMR method and its applicability for testing of silica-based HPA catalysts are demonstrated.A preliminary report of this work was presented to the Second European Congress on Catalysis EUROPACAT-II, Maastricht, The Netherlands, 3–8 September 1995.Deceased.     

The role of surface oxygen on copper metal in catalysts for the synthesis of methanol

Discrepancies in experimental measurements of adsorbed oxygen coverage on copper metal surfaces in working Cu/ZnO/Al₂O₃ catalysts are interpreted in terms of two types of adsorbed oxygen. The first, O(a), is identical with that observed in studies of single‐crystal copper surfaces. The second, O^*(a), not seen in single‐crystal studies, is more strongly bonded to the metal surface. It is suggested that the adsorption sites of O^*(a) contain Zn as well as Cu, from surface α‐brass (copper/zinc alloy) formation during catalyst reduction. Earlier experimental results on O(a) coverages on various supported copper catalysts are re‐assessed. Only catalysts containing Zn (or Ga) gave abnormally high coverages: with other supports, basic or acidic, O(a) coverages are less than ∼0.1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Enhancement of the Catalytic Activity of a Dawson-type Heteropoly Acid Induced by the Loading on a Silica Support

The Friedel–Crafts alkylation, benzylation of anisole with benzyl alcohol, was carried out over heteropoly acids (HPAs) supported on SiO₂. A Dawson-type HPA, in which Nb atoms were partially substituted with W atoms, exhibited the highest activity among various kinds of HPAs. The catalyst was reusable in the reaction after the filtration and it kept high activity even after the washing with hot water when the catalyst was calcined at 743 K. In contrast, the unsupported catalyst was almost inactive after the thermal treatment. The change in the activity was in good agreement with the degree in the acid amount measured by NH₃-TPD. Unlike the Dawson-type heteropoly acid, the activity of the Keggin-H₃PW₁₂O₄₀/SiO₂ remarkably dropped through the repeated use for the reaction. Based on the structural analysis of Dawson-type HPAs, the partially decomposed HPA on the support of SiO₂ was ascribed to the active species.     

Friedel–Crafts catalysis using supported reagents. Synthesis, characterization and catalytic application of ZnCl2 supported on fluoride‐modified sol–gel‐derived aluminosilicates

ZnCl₂–aluminosilicate catalysts were prepared via a sol–gel route involving fluoride‐catalyzed hydrolysis of aluminum and silicon alkoxides in the presence of NaF, KF, NH₄F and ZnF₂. The catalysts were characterized by employing ²⁹Si, ²⁷Al and ¹⁹F solid‐state MAS NMR. The dependence of the activities of the catalysts on the nature and amount of fluoride present in the catalysts were investigated using Friedel–Crafts alkylation reaction of benzene with benzyl chloride. This revised version was published online in July 2006 with corrections to the Cover Date.     

Comparison of the catalytic properties of Al‐ZSM‐22 and Fe‐ZSM‐22 in the skeletal isomerization of 1‐butene

The catalytic activities of Al‐ZSM‐22 (Al in the framework) and Fe‐ZSM‐22 (Fe in the framework) were compared in the skeletal isomerization of 1‐butene to isobutene. The catalysts synthesized in the laboratory were characterized by means of XRD, FTIR spectroscopy, SEM and surface area measurements. The activity of the zeolites was investigated using a fixed‐bed microreactor system. Al‐ZSM‐22 demonstrated higher activity in 1‐butene transformation compared to Fe‐ZSM‐22, while the selectivity to isobutene, on the other hand, was higher over Fe‐ZSM‐22. Coke formation was monitored using a microbalance and the results showed that the weight gain of Fe‐ZSM‐22 was slightly higher compared to Al‐ZSM‐22. This revised version was published online in July 2006 with corrections to the Cover Date.     

n‐octane reforming over alumina‐supported Pt, Pt–Sn and Pt–W catalysts

Pt, Pt–Sn and Pt–W supported on γ‐Al₂O₃ were prepared and characterized by H₂ chemisorption, TEM, TPR, test reactions of n‐C₈ reforming (500°C), cyclohexane dehydrogenation (315°C) and n‐C₅ isomerization (500°C), and TPO of the used catalysts. Pt is completely reduced to Pt⁰, but only a small fraction of Sn and of W oxides are reduced to metal. The second element decreases the metallic properties of Pt (H₂ chemisorption and dehydrogenation activity) but increases dehydrocyclization and stability. In spite of the large decrease in dehydrogenation activity of Pt in the bimetallics, the metallic function is not the controlling function of the bifunctional mechanisms of dehydrocyclization. Pt–Sn/Al₂O₃ is the best catalyst with the highest acid to metallic functions ratio (due to its lower metallic activity) presenting a xylenes distribution different from the other catalysts. The acid function of Pt–Sn/Al₂O₃ is tuned in order to increase isomerization and cyclization and to decrease cracking, as compared to Pt and Pt–W. This revised version was published online in July 2006 with corrections to the Cover Date.     

Partial oxidation of ethane to syngas over nickel‐based catalysts modified by alkali metal oxide and rare earth metal oxide

The catalytic activity, thermal stability and carbon deposition of various modified NiO/γ‐Al₂O₃ and unmodified NiO/γ‐Al₂O₃ catalysts were investigated with a flow reactor, XRD, TG and UVRRS analysis. The activity and selectivity of the NiO/γ‐Al₂O₃ catalyst showed little difference from those of the modified nickel‐based catalysts. However, modification with alkali metal oxide (Li, Na, K) and rare earth metal oxide (La, Ce, Y, Sm) can improve the thermal stability of the NiO/γ‐Al₂O₃ and enhance its ability to suppress carbon deposition during the partial oxidation of ethane (POE). The carbon deposition contains graphite‐like species that were detected by UVRRS. The nickel‐based catalysts modified by alkali metal oxide and rare earth metal oxide have excellent catalytic activities (C₂H₆ conversion of ~100%, CO selectivity of ~94%, 7 × 10⁴ l/(kg h), 1123 K), good thermal stability and carbon‐deposition resistance. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of model catalysts by laser interference nanolithography followed by metal cluster deposition

The extent to which metal particle geometry and adsorbate spillover influence the temperature‐programmed desorption spectra for the desorption of hydrogen from supported‐metal catalysts has been studied by Monte Carlo simulation. By including a mechanism for adsorbate spillover and surface diffusion it is shown that spillover of the adsorbate onto the catalyst support can result in the differences observed experimentally between desorption spectra obtained from single crystals and supported‐metal catalysts. An isosteric Arrhenius analysis of the TPD spectra has been used to demonstrate that, at low surface coverage, the activation energy characterising surface diffusion of adsorbates on the catalyst support can be obtained from the desorption spectrum. This revised version was published online in July 2006 with corrections to the Cover Date.     

Transition metal salts of heteropoly acids as palladium co-catalysts for Wacker oxidation of butene-1 to MEK

The transition metal salts of heteropoly acids have been applied as palladium re-oxidants in heterogeneous solid Wacker catalysts for the oxidation of butene-1 to MEK. Silica, γ-alumina and titania were used as supports for the Pd/MeHPMoV_x system. The influence of cations bonded to heteropoly anions and also the effect of the catalysts acidity on the butene-1 to MEK oxidation have been elucidated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Vapour phase O‐methylation of 2‐naphthol over the solid bases alkali‐loaded silica and Cs‐loaded MCM‐41

O‐alkylation of 2‐naphthol has been investigated in the vapour phase over alkali‐loaded fumed silica and Cs‐MCM‐41. Both SiO₂ and MCM‐41 had low C‐alkylation activities and no O‐alkylation activity. The introduction of alkali ions considerably increases 2‐naphthol conversion with 2‐methoxynaphthalene being the major product. The activity of the catalysts increases with alkali loading and the basicity of the metal (Cs > K > Na > Li). Very high conversion (∼99%) of 2‐naphthol and selectivity (>95%) for 2‐methoxynaphthalene are obtained over Cs‐loaded fumed silica and MCM‐41. A small amount of 1‐methyl‐2‐hydroxynaphthalene is also formed over the Li‐, Na‐ and K‐loaded silica. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nano‐pits: supports for heterogeneous model catalysts prepared by interference lithograpy

Nanostructured 4 inch Si wafers were prepared as new supports for model catalysts. A single wafer exhibits 10⁹–10¹⁰ pits on an otherwise flat silicon oxide surface. To produce these nanostructures, oxidized wafers were covered with photoresist material and exposed to laser interference patterns. Using hydrofluoric acid, wet‐chemical etching of the SiO₂ through the structured resist resulted in a pitted surface. The etched pits with diameters of 200–400 nm and depths between 50 and 70 nm were loaded with metal particles by evaporation (palladium, silver) or by means of spin‐coating (copper). Optimizing the methods enabled exact deposition of single metal clusters in the pits. The resulting model catalysts are remarkably stable against sintering, a major problem of conventional model catalysts when exposed to elevated temperatures and oxidizing gas atmosphere. The topography and chemical composition as well as their changes, induced by the reaction conditions applied, including stability and chemical behavior of the nanostructured systems, were investigated by means of AFM, SEM, temperature‐programmed methods and XPS. To determine their usefulness in catalysis, specially designed reactors were developed for catalytic investigations. This revised version was published online in June 2006 with corrections to the Cover Date.     

Gas‐phase pinacol conversion on AlPO4, γ‐Al2O3 and SiO2 catalysts

Pinacol (2,3‐dimethyl‐2,3‐butanediol) conversion over AlPO₄ (Al/P = 1) and γ‐Al₂O₃ catalysts proceeded in two parallel reaction pathways with formation of 2,3‐dimethyl‐1,3‐butadiene (by 1,2‐elimination) and 3,3‐dimethyl‐2‐butanone (by rearrangement), the latter being the main reaction product. The activity was in accordance with the surface acidity data as measured versus cyclohexene skeletal isomerization reaction. Thus, AlPO₄ showed the highest activity (almost total conversion at 523 K). The 1,2‐elimination/rearrangement ratio depended on the type of catalyst used and diene formation increased with reaction temperature. Moreover, pinacolone was a reaction intermediate for diene production. This revised version was published online in July 2006 with corrections to the Cover Date.     

Metal nanoclusters supported on metal oxide thin films: bridging the materials gap

Characterization and reactivity studies were performed on model catalysts comprised of metal clusters supported on metal oxide thin films. The thin films are prepared by vaporizing the parent metal onto a refractory metal substrate in an O₂ environment. The oxide films are sufficiently conductive via defects and tunneling to the substrate that the use of charged particle spectroscopies does not lead to any adverse charging effects. Numerous characterization techniques demonstrated that both spectroscopically and chemically these thin films are comparable to the analogous bulk metal oxides. Model supported catalysts were subsequently prepared by vapor‐depositing catalytically‐interesting metals onto these thin film oxide supports. This deposition method realizes tight control over cluster size and, therefore, represents an ideal approach to studying size‐dependent chemical and physical properties. Reactivity studies established the validity of the supported systems as models of conventional catalysts. Furthermore, the use of these model catalysts provides a bridge between fundamental studies of single crystal reactivities and applied studies of high‐surface‐area catalyst activities. This revised version was published online in June 2006 with corrections to the Cover Date.